Catalytic addition of cyanogen halides to olefins



Patented Sept. 29, 1953 2,653,963. CATALYTIC ADDITION or- CYANOGEN HALIDES T OLEFINS Frank M. Cowen, Norwalk, and James K. Dixon, A Riverside, Conn., assixnors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application April 12, 1951, Serial No. 220,726

The present invention relates to a novel method of preparing nitriles.

It is an object of the invention to prepare nitriles by reacting a cyanogen halide with an olefin in the presence of a catalyst. It is a further object of the invention to prepare halonitriles and/or unsaturated nitriles by the aforesaid reaction. It is a still further object to prepare nitriles from inexpensive raw materials.

Various attempts to react cyanogen halides with olefins have been made in the past without success. The present invention is based on the fact that the addition is made in the presence .of a catalyst. The preferred catalyst for the reaction is a complex resulting from the admixture of aluminum chloride with nitrobenzene. However, various other catalysts may be used such as the 14 Claims. (01. 260-464) complex resultin from the combination of aluminum chloride with nitromethane or aluminum bromide with nitromethane or nitrobenzene, or boron fluoride with nitromethane or nitrobenzene.

It has been found that the complex resulting by 1 and even more preferably about -55 C. In

either case the reaction product is generally a mixture of halonitriles and unsaturated nitriles.- which products can be separated and recovered Depending on theby fractional distillation. nitrile mainly desired, the reaction can be con ducted at temperatures as low as 0 C., or even lower, and as high. as the boiling point'of the nitrohydrocarbon used (for example-ashigh as 255 C).

2 It is also postulated that the reactions may proceed as follows:

In the Equations 1, 2 and 3 each R is hydrogen, a parafiinic hydrocarbon residue, or a terpenyl residue,'and the Rs can be the same or different, and can be joined to form a cyclo-olefin, and X is either chlorine or bromine.

The invention also contemplates the addition of' cyanogen chloride or bromide to substituted olefins in which the substituent groups do not aifect the activity of the double bond to any marked degree, as for example, the halo-olefins and the like.

In the course of the reaction various side products are formed. The various components in the final reaction mass are conveniently separated from each other by fractional distillation.

: The fl-chloronitriles are useful intermediates in the preparation of polymers, the fi-chlorocarboxy acids, and a-fi-unsaturated acid derivatives.

The unsaturated nitriles are useful intermediates in the preparation of polymers, for example guanamine resins, and unsaturated carboxy acids.

. The nitriles are also effective as selective solvents Some unsaturated nitrile is generally obtained (along with halonitrile) below 25 C.,

and some halonitrile is generally obtained (along with unsaturated nitrile) above 25 C. I

The overall reaction contemplated proceeds as can be the same or different, and can be joined to form a cyclo-olefin, and X is either chlorine or bromine.

for separating the components of lubricating oils.

The following examples illustrate but do not limit I the invention.

; EXAMPLE 1 'A'dditiohof cyanogen chloride to Z-butene .is-conveniently carried out in the reaction vessel in? which the cyanogen chloride and olefin are to be reacted. In this particular example, a. 1- liter S-neclred round bottom flask can be used.

following the addition of cyanogen chloride. 2-;

butene is bubbled into the mixture through a still maintaining the temperature 1 C;

The mixture is stirred as bya'neleotricaflydriven' stirrer placed directly over the sintered disc. A

thermometer is inserted into one ot the necks I together with a condenser, to which is attuned 1 a drying tube filled with a desiccant. The whole assembly is preferably placed in a well-ventilated area.

After 1% home the addition 0! olefin is discontinued, but the reaction mixture is kept at 0-5 C. for hours and then the temperature is allowed to rise slowly to room temperature overnight with s'tirr'ing.

The product is worked up in a manner analogous to Friedel-Crafts reaction masses, e. g., the product is poured, with stirring. over a, liter of cracked ice containing a little concentrated hydrochloric acid to hydrolyze the product-catalyst complex. (It is notabsolutely-necessary that the I-ICl be present, but it accelerates hydrolysis.) After standing for about an hour; the carbon disulfide-product Iayer is-separated h'om the aqueous layer. The latter is extracted with three l0 sintered glass disc as rapidly n possible, willie v 4 150-00. portions of ether and the ether extracts and carbon disulfide-product layer combined and dried over a desiccant.

'I-he produd I filtered free at 'dryim agent ald-lubiielftad toa low lamslure distillation until all ether and carbon disulfide has been removed. The brown 011 (110 g.) that remains is distilled through a 1 x 12 inch rectifying column with the following results:

=.Il.P,'1 .mm. Wt m. mic Hg Pl'OdllCt 32 7 Nitromethane.

2 cis-2-Methylcrotononitrile. 30 2 trans-2-Methylerotononitrile. 4...-.-. ,.-.c.- 69-73 l5-l6 61 3-Cliloro-2-metliylbutyronitrile. High boilers and 67 H 48 Mixture of nitrile polyresidue. mers and olefin polymerauseiul-as-mln or waiting agent :iniermediates.

'nie 51 g. ofi3 chloro-2-mwthy lbutyronitrile necovered m Example 1 corresponds to a yield of 43%..

Infeadhfl the herein examples cyanogen bromide is substitutable 1mcmogen chloride, "and vice versa.

Using a procedure analogous to that -of Exampie 1, various other beta-"halonttrlles can be pre- The foilow'ing table is illustrative of a few or the :ole'fln's, solvents, and products. together with the yield in each instance.

BE'DA-CHLORONIIBILES 'PRODUCED BY THE ADDITION OF 'CYANOGENCHLORI'DE TDOL'EF'INB (detailsln f'm) Olefin Solvent modulate) 3,3 tag- 5 Tropyiene Cs, CHaC'HClCHzCN 6 awn/11.5.

l-Buten'e c n??? oniomoaolomox l8 '5959.5l5-6.

mum cs, cmorrolomomcm 43 M. Oyclohuno..-....-..,i Monochloroben-i trans 15 79/2-3.

zone.

I 01 m if) -90-92/3.

i ocummun es, C'HKCHMOH'CICmCN 9 sass/1.5.

iinoamm -CB;(CH:).C'HCIC'H1CN s nae 1.

UNB'ATURIQTED NIT-RIDES PRODUCED BY THE ADDITION OF C'YANOGENCELORIDE 'IO OL'EFINS .(details infra) oienn -Eroduct(s) Z, YiekLPeroantg 3.1 C./mm.Hg

Propylene 4 m -1ll-6.

om o nxo-non l-Butene eta-Him: 1 425-143.

V omcmo =CHCN v Mintoue .1 cis-i-trans -5. 122430.

oHioH=ooN U HI 'flnlohmncnuucni CN 2i 5413.

4mm... and. .ss dos- 2, CH|(GH1).CH=CHCN; '9 I l-Dodeoclc y 7 ds-Ham tand 5,1 ..i W land-981991,: 1 onxomhcn-cnon I EXAMPLE 2 OICN CHaCH=CHz CHaCH=CHON -I- HCl A previously prepared, cold solution of 90 g. of anhydrous aluminum chloride, 75 ml. of nitromethane, and ml. (0.5 mol) of cyanogen chloride is poured into a 300 ml. precooled (5-10 C.) autoclave. The autoclave is closed, and 60 g. of propylene slowly introduced into it at a temperature ranging from 20-35 C. over a period of 3% hours. The pressure during this time varies within the range of 18-123 p. s. i. The autoclave is then cooled, vented, and opened, and the product is removed'and poured on a mixture of ice and concentrated hydrochloric acid. The mixture is stirred and extracted with ether. The ether extracts are separated, shaken with a cold sodium hydroxide solution, and dried over a sodium sulfate desiccant. The residual ether and nitromethane are removed by distillation, and the remaining product comprises 7.5 g. (15%) yield of B-chlorobutyronitrile, B. P. 6364 C./ 13 mm. and 2 g. (6%) yield of cisand trans-crotononitrile, B. P. up to 40 C./ mm. This recovery thus represents a total yield of 21% of identifiable nitrile, based on the amount of cyanogen chloride used as a starting reactant.

EXAMPLE 3 Addition of cyanogen chloride to cyclohexene To a suspension of 90 g. (0.675 mol) of aluminum chloride in 150 cc. of monochlorobenzene, cooled by a water bath at about room temperature, is added 48 cc. of nitromethane slowly with stirring, following which'the aluminum chloride dissolves. The solution is then cooled to about 0-10 C. and 28 m. (0.55 mol) of cyanogen chloride vaporized into this solution through a submerged inlet tube. addition of 0.5 mol of cyclohexene through a dropping funnel is begun, and is continued for about 1 hours, while stirring the mixture and maintaining it at a temperature below 10 C.

Thereafter no more cyclohexene is added, and the temperature of the reaction mass is permitted to rise slowly to room temperature. The product is then pouredfwith stirring, over a liter of cracked ice containing a little concentrated hydrochloric acid. The chlorobenzene-product layer is sepa- EXAMPLE 4 Preparation of p-chlorobutyronitrile and crotononitrile To a suspension of 180 g. (1.35 mols) of alumi- I num chloride in 250 cc. of carbon disulfide, cooled by a water bath, is added 68 cc. (1.25 mols) of nitromethane, slowly with stirring, following which the aluminum chloride dissolves. The solution is then cooled to 0-10 0., andonemol Immediately thereafter the --(5 2' cc.) of cyanogen chloride vaporizedinto the solution through asubmerged inlet tube. -Immediately thereafter the addition of the propylene through a sintered glass disc is begun, and is continued for about 1 hours, while stirring the mixture and maintaining it below 10 C. Thereafter no more propylene is added, and the temperature of the reaction mass is permitted to rise slowly to room temperature. The product is then poured, with stirring, over a liter of cracked ice containing a little concentrated hydrochloric acid. The carbon disulfide-product layer is separated from .the aqueous layer, the latter is extracted with ether, and the ether extracts and the carbon disulfide-product layer are combined and dried over a desiccant. The product is illtered and fi-chlorobutyronitrile is separated therefrom by fractional distillation in a yield of 6%. Crotononitrile (cis and trans) is also separated from the productby fractional distillation in a yield of 1%.

EXAMPLE 5 Preparation of .fl-chlorovaleronitrile and pentenonitrile I about 1%; hours, while stirring the mixture and maintaining it below 10 C. Thereafter no more l-butene is added, and the temperature of the reaction mass is permitted to rise slowly to room temperature. Theproduct is then poured, with stirring, over a liter of cracked ice containing a little concentrated" hydrochloric acid. The carbon disulfide-product layer is separated from the aqueous layer, the latter is extracted with ether,

' and the ether extracts and the carbon disulfideproduct layer are combined and dried over a desiccant. The product is filtered and 'p-chlorovaleronitrile is separated therefrom by fractional distillation. Yield, 18%. A' mixture of cisand trans-Z-pentenonitrile is also separated by fractional distillation. Yield, 7%.

EXAMPLE 6 Preparation of 8-chloropelarogononitrile and nonenonitrile To a suspension of 180 g. (1.35 mols) of aluminum chloride in cc. of carbon disulfide, cooled by a water bath, is added75 cc. of nitromethane, slowly with stirring, following which the aluminum chloride dissolves. The solution is then cooled to 0-10 C., and 56 cc. (1.1 mols) of cyanogen chloride is vaporized into the solution through a submerged inlet tube. Immediately thereafter the addition of 112 g. (1 mol)'of 1- octene through a dropping funnel is begun, and is continued for about 1 hour, while stirring the mixture and. maintaining it below 10 C. Thereafter no more octene is added, and the temperature of the reaction mass is permitted to rise slow- 1y to room temperature. The product is then poured, with stirring, over a liter of cracked ice a fl l ttle "cdfieentra" dric acid. 'I'he carbon dc-Drdduct" ayer is 'sebfara'ted from the aqueofi's layer, the latter *ls extracted with "ether, the ether 'esitra'etsand the carbon disulfide pr'oairet iayer aremmet 'an'rl-dried-over a'de'siccafit. fa l-1e and p ehloropelairo'g'oi'ionftriie istifaifated therefrom by "fractional seamstress. 9%. it mixture of cis--and trahs-fi-hdrienehitrile is also separated therefrom by fractional distillation. Yield-15%. H

Preparation of p-chloro tridcdnohitfile 'ahd 'fiidecenonitrile To a suspension r iao g. 41.35 mols) cramminum chloride in 150 ecfdf carbon disulfidmooold by'a water bath, is added 75 of nitromethane, slowly with stirring, followin'g which 'alufnichloride 'iiissolvee. The solution is then cooled to 010 C. and 1.1 mols (56 co) or'eyemogen chloride is vaporized into this solution through a submerged inlet tube. Immediately thereafter the *saaim'n 168 "g. (new "of 1- dodecene through a dropping funnel is begun, and is continued for about 1 hour, while stirring the -nii'irtiire and maintaining 'itat'a temperature belbvvlO" c. 'Tliieaftei- 'no'iiioie do'decerie isiadde'd, and-me temperature o! the reaction permateatonse sliiwlyto temperature. The

product is then poured, with "stirring, over a liter of cracke ice eo'njmmmk a little coneehtrated hydrochloric acid. v The carbon 'disu'lfide :praduet layer 'is 'se ar tea rromfme aqueous layer. the latter is extracted with ether.arid the "ether -extracts and the flea-risen di's'ulflde pr'odiict isyer comiim a and ariea'dver adesicca'r'it. 'The'pr'od- 116i; ls flltefd" lild fl bmdfbtl'ldediflmiiflfilg sep- 81%. A mixture aresash trains-'ztridecanonfitnle also separated therefrom by "fractional distillation. Yield. 9%.

aeration af'c mio'aen Urofnidetodipehfen'e To a suspension of 360g. 1:35; mols) of aluminum bromide in -150 0c. of carbon; disulflde is added 75 cc.- of nitroinethane, slowly withstirring, following which the aluminum bromide dissolves. One mol 106 g.) of cyanogen -bromide;powde r added to the solution and-immediately thereafter the addition of -dipentene is begun through a dropping funnel. i

One mol of dipentene-is thus added-dropwise, with stirring. The reaction is then discontinued, the product is pouredfwithstirring, over a liter of cracked ice containing a little concentrated hydrochloric acid. The carbon disulfi'de-produet layer is separated from the aqueous layer, the latter is extracted-*with ether, and the"ether extracts and the carbon disulflde-pi'odut layer combined and dried"6ver a"desicoant. "The product ls filtered anda mii'cture of the various addition productsof -the following i'oririulae-is sep- 'arated from the residual w fractional -*dis- -tillation.

'cin'nr on. em B:

EXAMPLE Q atkfiition of-cyanogen bromide to marten To a suspension 'of 360 g. (1.3 5'1nols') of al uminum bromide in 250 cc. of carbon disulfide is added -68 cc. (l-.25 mols) of nitromethane, slowly with stirring, following which the aluminum bromide dissolves. One mol (106 g.) of cyanogen bromide powder is addedtothe solution and im- 'fnediately thereafter the addition of dipentene is begun through s. dropp rumiel.

One'mol of dipentene is thus added 'dropwise, 'with stirring. The reaction is then discontinued, *the product is poured, with stirring, over a liter of cracked ice containing a little concentrated hydrochloric acid. The carbon di'sulfide-product layer is separated from the aqueous layer, the latter is extracted with ether, and the ether extracts and the carbon disulflde-product layer =combined and dried over a'desiccant. The prodnet is filtered and a mixture of various unsatura't'ed cyanodipentenes separated from the re- "sidual hiass by fractional distillation.

EXAMPLE 10 Preparation of -2-bromo-1-cydn0c1/cl0hexane and c'yanocyclohezene While'it is generally preferred to conduct the addition of cyanogen bromide to an olefin in the presence of an additional solvent, it is not absolu'tely necessary, as shown b'y'the' follo'win'g *example.

1 mol (106 -g.) of cyanogen bromide 'is added to a cooled solution of 360 g. (1.35 mols) of aluminum bromide in 400 cc. of nitrobenzene, slowly with stirring. The mixture is cooled to O -10 C. and'102-cc. (1 mol) -of cyolohexeneis-added'dropwise through -a dropping funnel, with stirring over a .period of /2 hour. The stirring is continued for 4 hours at 0-10 C. after the addition is complete, and then overnight at room temperature. The resulting reaction mass is then poured, with-stirring over a liter of cracked 'ice containinga-little concentrated hydrochloric'acid. The resultant ;aqueous layer is extracted with ether and dried over-a desiccant. The product is then filtered and --2-bromo-l-cyanocyclohexane and -cyanocyclohexene are obtained therefrom by iractional distillation.

.E X 'A'BIPI'E .11

Preparation of fi-bromopeloraaononit'rile and nonenonitrile 'To a'soliition-of 360-g. (135:mo1s) o'faluminum bromide in 'cc. or 'hitromtliarie is'added 106 "g. (1 men of cya no'gen bromide, with stirring. g. (1 mol) of l-octene -'is added dropwlse through a dropping tunnel 'with stirring, over a period of approximately one hour at (IF-5" C. h tter the addition -ls complete, the stirring is "continued for 4hours'at'0-'1'0 C. and then'ov'ernight at room temperature. The product is poured, 'withstir ring, over a liter ofcra'cked ice 'cbntaining alittle concentrated'hydrochlorlc acid. The aqueous layer is extracted with ether, the ether extract is dried'over a desiccant, and the product is filtered and fi-bromopelarogononitrile "and nonen'onitrile are separated therefrom by fractional distillation.

Preparation of2-bromo-1-cyanocyclohexane and cyanocyclohexene ro-a suspensionof-3 6 0-g. (1.35'triol's) crammi- 'bromlde in 250 cc. or carbon disulfide =is smarts .9 added 200 cc. of nitrobenzene, with 'sti'rrihgffol lowing which the aluminum bromide dissolves; The solution is cooled and one mol (106 g.) of cyanogen bromide powder is then added to the cooled catalyst complex and-immediately thereafter the addition of 102 cc. (1 mol) oi. cyclohexene is begun through a dropping funnel with stirring. The cyclohexene is added-over a period of hour at l0 C., and the stirring is continued for about 4 hours at 0-l0 C. thereafter and overnight at room temperature. The reaction is then discontinued and the product is poured with stirring over a liter of cracked ice containing a little concentrated hydrochloric acid. The carbon disulfide-product layer is separated from the aqueous layer, the latter extracted with ether, and the ether'extraot and the carbon disulfide-product layer combined and dried over a desiccant. The product is filtered and 2-bromo-1-cyanocyclohexane and cyanocyclohexene separated therefrom by iractional distillation.

EXAMPLE 13 Preparation of fl-chlorovalero'nitrile and pcntenonitrile A previously prepared, cold solution of 90 g'. of anhydrous aluminum chloride, 100ml. of nitrobenzene, and 26 ml. of cyanogen chloride is poured into a 300 ml. precooled autoclave. The autoclave is sealed, and 56 g. of l-butene slowly added at a temperature ranging from 20-35 C. over a period of about 3 /2 hours. The autoclave is then cooled, vented, and unsealed, and th product removed and poured on a mixture of ice and EXAMPLE 14 Preparation of fi-chloropropionitrile and acrylonitrile A previously prepared, cold (less than C.) solution or 90 g. of anhydrous aluminum chloride, '75 ml. nitromethane, and 26 ml. (0.5 mol.) of cyanogen chloride is poured into a 300 m1. autoclave, precooled to 0-10 C. The autoclave is sealed, and 46 g. of ethylene slowly added while maintaining the temperature below 10 C. The addition is preferably carried out over a period of about 3 to 4 hours. The autoclave is then cooled, vented, and unsealed, and the product removed and poured on a mixture of ice and concentrated hydrochloric acid. The mixture is stirred and extracted with ether. The ether extracts are separated, shaken with a cold sodium hydroxide solution and dried over a sodium sulfate desiccant. The residual ether and nitromethane are removed by distillation, and B- chloropropionitrile and acrylonitrile separated from the remaining reaction mass by fractional distillation.

EXAMPLE Preparation of 3-chloro-2-methyZbut1/ronitrile and Z-methylcrotononitrile Nitrobenzene (200 ml.) is added dropwise to 90 g. (0.675 mol) of aluminum chloride. The mixture is stirred rapidly from the beginning. With 1'0 occasional external cooling by means'oi a water bath, the temperature is gradually allowed to rise to 55 C., at which point the aluminum chloride completely dissolves, giving a clear orange solution. This solutionis then cooled to 05 C., converting it to a thick slurry of solid complex and nitrobenzene. Into this slurry is vaporized 29 ml. (0.55 mol) of cyanogen chloride througha glass tube. Immediately thereafter, 2-butene is bubbled through a sintered glass disc into the mixture as rapidly as possible while still maintaining the temperature of the reaction mass 'below about 10 C. After about 3 hours the addition of olefin and the stirring are discontinued, and the reaction mass allowed to warm gradually to room temperature. The result is a red solution. This solution is poured on a mixture of crushed ice and concentrated hydrochloric acid, and the result is stirred and allowed to stand for a few minutes, after which the product layer is separated from the aqueous layer.- The aqueous layer is then extracted with three 150 ml. portions of ether and the extracts and the product layer combined. This combination is extracted with a dilute sodium hydroxide solution and dried over sodium sulfate to give an orange solution, from which the ether is distilled off. Two fractionations of the residue give a 37% yield (24 g.) of 3-chloro-2emethylbutyronitrile, and a 20% yield (9 g.) of mixed cisand trans-2-me'thylcrotononitriles. The total yield 01 identifiable nitriles is thus 57% (based on cyanogen chloride).

Preparation of 3-chloro-Z-methylbutyronitrile and Z-methylcrotononitrile 200 ml. of cold (about 10C.) nitromethane is saturated with boron triiluoride, with rapid stirring, and about 70; g'. of the latter is absorbed. The resulting solution iscooled to about 0-5 C. and 52 ml. (1 mol) of cyanogen chloride isvaporized into itthrough'a'sintered glass disc, with stirring. vExcess 2-butene is bubbled through the solution for about 3" hours as rapidly as possible while the reaction mass is maintained at a temperature below 10 C. The stirring and olefin addition are then stopped and the reaction mass allowed to rise slowly to room temperature. The result is an orange solution which is poured on cold water and extracted with ether. The ether extracts are shaken with cold dilute sodium hydroxide solution and fractionated. Yield, 3 g. of 3-chloro-2-methylbutyronitrile, and 5.5 g. of a 1rnilxture of cisand trans-2-methylcrotononir1 es.

EXAMPLE 1'7 Preparation of 3-chloro-2-methylbutyronitrile and Z-methylcrotononitrile g. of nitrobenzene is saturated with 10 g. of boron trifluoride and the solution mixed with 164 g. of boron trifiuoride etherate. By a procedure similar to that used in the previous example, 1 mol of cyanogen chloride and excess 2- butene are added. Following the recovery method of the previous example, one frame of 3-chloro-2-methylbutyronitrile and one gram of 2-methylcrotononitrile are obtained.

Whil the invention has been described with particular reference to specific embodiments, it is to be understood that it is not to be limited thereto but is to be construed broadly and restricted solely by the scope of the appended claims.

This application is a continuation-in-part of 11 U. S. Serial Nos. -88,69 4 'and ;fl8r6 il5, April 20, 1949,;both nowabandohed.

We claim:

1. The method of preparing al alo :nitrile comprising sub'jectingan oleflnqto oha member of the group consistingof' cyanogen chloride and cyanogen bromide-in the presence of a catalyst selected from-the group consisting; of aluminum chloridemitrohydrocarbon, aluminum bromide-nitrohydrocarbon, and boron-trifluoridenitrohydrocarbon combinations, at e=temperature not substantially exceeding the'boilinghpoint' of the nitrohydrocarbon.

2. The method of preparing a chloronitrlle that comprises subjecting'anoleflnto the: action otcyanogen chloride in I the presence 01' a' catalyst selected' from the grouplconsisting of: aluminum chloride-mltrohydrocarbon, aluminum. bromiden'itrohydrocarbon, andboron t'rifluoride-nitrohyidrocarbon combinations, aUQt'CmDCZGtUIE-DOVCX ceeding about 25 C.

3. The" method of reparlng'a fihalo -nltrile that comprises subjecting-'amolefln to the-section of a member of the group conslstin'g of cyanogen chloride and cyanogen bromide -in' the--presenoe ofa catalyst consisting eta-combination '1" aluminum chloride and a'nitrohydrocarbon.

4'. The method according to-clai'm 3 in which the nitrohydrocarbon is a 'nitroalkane;

5. The methoda'ccording to claim 3 in which tbrthemcttcmchcy mhlnride at atemper- Widow-i2 1G. in themreseme of a catalyst allminumtchloride and nitromethane. wherebycamethyhohlombuwromtrile :is termed.

lor'lhe-kmthod subjecting cyclohmnekto (the: action. 012 cyanogen 'chloride at a tempgmturgehelowflfi C..in=the-presence of a cataly t mm'prilinzcaluminum chloride and nitronQatWhfl b! fl-qchlom tecyamcyclohexane 1811M.

-11-.:frhe eomnminaubi tins pr pylene-ito-rtheraptiongoi cyanogenchloride at a -temparature'-below- 25 6. in the-r presence 01 a mt commuting :a-luminum.-.chloride-and nitromethane; whereby. ifl-sohlorobutyromtrile is formed;

12;:Ther method: 501. 10mins pentenonitriles comprisingfisubjflting mbutene-tot theaction oi cyamneu' chloride at1 a temperature of at least 'afifrcsimthe presmoecialuminum chloride and 111mm.

13. The method 01 forming crotononitrile comprising subjecting. propylene to the action of cyanogen chloride at a temperature of at least 25 C. in the presence of aluminum chloride-and nitromethane.

14. The method otiormingan unsaturatedni- ,trilecomprisingsubjecting an.olefin to the action of cyanogen chloride .inithe presence 01' a catalyst .of the groupconsisting of aluminum chloridenitrohydrocarbon, aluminum bromide-nitrohydrocarbonnand boron triflunrid'eenitrohydrocaribon combinations at atemperature of at least 25 C.

FRANK M. COWEN. JAMES K. DIXON.

.ReIerences Cited in the file of this patent STATES PATENTS Number Name Date 2,402,878 Coflman et a1. June 25, 1946 2119388- Dutcher Apr. 22, 1947 2,422,859 Schulz-e et a1 June 24, 1947 

1.THE METHOD OF PREPARING A HALO-NITRILE COMPRISING SUBJECTING AN OLEFIN TO THE ACTION OF A MEMBER OF THE GROUP CONSISTNG OF CYANOGEN CHLORDE AND CYANOGEN BROMIDE IN THE PRESENCE OF A CATALYST SELECTED FROM THE GROUP CONSISTING OF ALUMINUM CHLORIDE-HITROHYDROCARBON, ALUMINUM BROMIDE-NITROHYDROCARBON, AND BORON TRIFLUORIDENITROHYDROCARBON COMBINATIONS, AT A TEMPERATURE NOT SUBSTANTIALLY EXCEEDING THE BOILING POINT OF THE NITROHYDROCARBON. 